Block copolymers are emerging as a fascinating materials for understanding and controlling processes associated with optoelectronic devices. The self-assembly induced by block copolymer is a reliable and powerful technique for advanced nanopatterning to fabricate nanomaterials of different functionalities for optoelectronic devices. This technique is particularly promising for pushing the boundaries of block copolymer lithography and creating a unique surface architectures or ‘superstructure’ and complex morphologies at the nanoscale. Microphase separation of BCP generates a highly ordered and tunable periodic nanoscale structures like spherical, lamellae, gyroid, and cylinders through self-assembly process. The association of small organic molecules with complementary recognition unit have the active sites with one of the blocks of BCP along the chain. This association approach of small organic molecules with BCP is known as block copolymer supramolecular strategies. The well-defined microphase separation of the BCPs induce the controlled assemblies of the small additive molecules into nanoscopic length scale inside the BCP microdomains. Therefore, BCP supramolecular strategies are effectively considered to tailor the physical properties, such as optical, luminescence, electronic, etc. of the functional small molecules via controlling their aggregation, as these properties significantly depend on their superstructure morphology and make it easier to understand the enhancing of device performance.